The H.I.V.E. Five were first encountered as a group robbing a mall. The Teen Titans tried to stop them but the H.I.V.E Five easily defeated them. They came close to killing the Titans but were driven off by Mother Mae-Eye. Though they did not get away with any crimes in the end, they still took pride in beating the Titans. They happily celebrated their victory in their base afterwards. However the Titans later returned the favor by sending them Mother Mae-Eye's cursed pie, which possessed them. During this episode the members of the H.I.V.E Five were Private H.I.V.E., Jinx, Mammoth, Gizmo, and See-More.

The H.I.V.E Five reappeared after Private H.I.V.E. had left the company of the others and was replaced by Billy Numerous and Kyd Wykkyd. They robbed a museum containing Egyptian artifacts, but were foiled by the young superhero Kid Flash, who had taken a liking to the H.I.V.E Five leader Jinx. Jinx tricked Kid Flash and, together with her comrades, succeed in capturing him. When they tried to present Kid Flash to Madame Rouge of the Brotherhood of Evil, Kid Flash escaped and the entire team ended up humiliated and scolded by Rouge. Madame Rouge went after Kid Flash herself, with Jinx also taking up pursuit. The other H.I.V.E Five members were afraid of Madame Rouge, so they decided not to take part in the mission.

Rouge located and attacked Kid Flash, who barely managed to find safety in a warehouse. However, Jinx arrived on the scene momentarily and trapped him with a device made by Gizmo. Jinx showed Madame Rouge her catch with pride, but Rouge once again patronized her, so in retaliation Jinx allowed Kid Flash to escape and struck back against Rouge. While this feat finally impressed Rouge, it was too late; Jinx renounced her criminal career and left the H.I.V.E. Five.

The H.I.V.E Five later on participated in the final battle against the Teen Titans in the Brotherhood of Evil's base. When the Five decided the fight was lost and attempted to turn tail, Jinx appeared alongside Kid Flash, and beat her former teammates with relaxed ease. They were subsequently flash frozen along with the other members of the Brotherhood of Evil.

The H.I.V.E Five team changes their members almost every time they appear. Jinx, Gizmo, Mammoth were permanent members of the team (starting out as just "The HIVE" with Gizmo, Jinx, and Mammoth. Then in Lightspeed they were six as Private H.I.V.E. had left them since Mother Mae-Eye, and was replaced by Billy Numerous and Kyd Wykkyd. Jinx left at the end of episode Lightspeed and was seen paired with Kid Flash and fought against the H.I.V.E Five during Titans Together). Almost all of the H.I.V.E. Academy students were a part of the H.I.V.E. Five at some point in the series except for XL Terrestrial, I.N.S.T.I.G.A.T.O.R., Wrestling Star, Rock, Paper, Scissors, Bumblebee, and the various hooded students seen.

Jinx'' (formally): The leader of the H.I.V.E Five near the end of the series. She wields powerful bad luck powers, and is also a good gymnast, capable of performing flips and jumps. She was the apparent leader of the team, until she left.

Gizmo: A short boy genius who has an arsenal of mechanical tools and weapons. Gizmo is also a good hacker, easily breaking into computer systems. In the comics, he is the second leader of the H.I.V.E. Five.

Mammoth: The big "muscle" of the group. Mammoth is very strong and "thick-skinned", making it hard for him to feel pain. He can produce massive shockwaves with his arms. Opposite of Gizmo, he lacks some mental capability.

See-More: A one-eyed villan who joined prior to the episode Mother Mae-Eye. See-More's powers come from a single eye-visor on his helmet, which mounts various "eyes" with various super abilities. His powers include shooting eye shaped bubbles like projectiles, making shields, X-ray vision, and heat tracking. It is possible that he left the group while still trailing along the path of evil at the end of Lightspeed because Jinx left.

Private H.I.V.E: A military borned fighter who joined prior to Mother Mae-eye, but left before Lightspeed. Private H.I.V.E is a strong hand-to-hand fighter who prefers to defeat his enemies with brute force. His main weapon is his shield, and he uses it in a similar manner to Captain America. In the comics, he left the H.I.V.E. and refuse to take orders from anyone anymore, and later decided to change his ways.

Billy Numerous: An evil, cloning teenager who joined prior to Lightspeed. Billy Numerous can create numerous clones of himself (hence the name Numerous). These clones have the same abilities he has, but they are independent entities, so Billy cannot control them, but they usually think the same as he does anyway.

Kyd Wykkyd: The quiet stealth master who joined prior to Lightspeed, replacing Private H.I.V.E. Kyd Wykkyd is the silent member of the team. It's unknown if he's mute or simply chooses not to speak, but most likely he is not because he was seen laughing. He is capable of teleportation, which allows him to perform sneak attacks. He also is capable of physical fighting, but he uses his sharp cape instead of his fists and feet. His cape has been proven to be strong enough to cut through steel. His costume resembles Batman's.

During Jinx's leadership, she tended to say battlecries such as "H.I.V.E Five; eat 'em alive!" or "H.I.V.E Five; rob 'em blind!" (which doesn't even rhyme). They seem to almost be parodies of the Teen Titans' "Titans, GO!".